CN109661707A - The manufacturing method of electrocondution slurry and its manufacturing method and solar battery - Google Patents
The manufacturing method of electrocondution slurry and its manufacturing method and solar battery Download PDFInfo
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- CN109661707A CN109661707A CN201780054325.XA CN201780054325A CN109661707A CN 109661707 A CN109661707 A CN 109661707A CN 201780054325 A CN201780054325 A CN 201780054325A CN 109661707 A CN109661707 A CN 109661707A
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
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Abstract
A kind of electrocondution slurry is provided, it includes the electroconductive powder containing silver, indium powder, silver-colored tellurium cladding glass powder, solvent and organic bonds, above-mentioned silver tellurium cladding glass powder is that have on the surface of the tellurium glass frit of the tellurium containing 20 mass % or more and coat glass powder with the silver-colored tellurium of silver and tellurium clad as main component.
Description
Technical field
The present invention relates to it is a kind of be suitable for the electrode slurry material as solar battery electrocondution slurry and its manufacturer
The manufacturing method of method and solar battery.
Background technique
Back and forth, the electrode slurry material as the solar battery comprising the semiconductor using pn-junction, using containing
There is the electrocondution slurry of silver powder, adhesive, solvent, frit etc..Using such electrocondution slurry, in the light-receiving surface of solar battery
The wiring of the surface electrode using silicon nitride to form arbitrary graphic pattern on the anti-reflection layer of representative of side.
In these, a kind of electrocondution slurry is proposed, by using the tellurium system frit comprising tellurium oxide as frit
(hereinafter, otherwise referred to as " tellurium glass frit "), is attached (otherwise referred to as to reduce by anti-reflection layer and semiconductor
" burn (fire through) ") when resistance, obtain good characteristic of solar cell (for example, referring to patent document 1).
In addition, proposing a kind of electrocondution slurry, contain a kind of metal or metal in Ti, Bi, Zn, Y, In and Mo
Thus the attritive powder of compound can form the surface electrode with high conductivity and excellent bonding force (for example, referring to patent
Document 2).
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2011-96747 bulletin
Patent document 2: Japanese Unexamined Patent Publication 2005-243500 bulletin
Summary of the invention
Problems to be solved by the invention
As the electrode applications of solar battery, seeks to further decrease contact resistance, obtains good solar battery
The electrode slurry material and electrocondution slurry of the solar battery of characteristic.
Problem of the present invention is that solving previous above-mentioned problems, reach following purpose.That is, the purpose of the present invention
It is, provides in the case where the electrode applications for solar battery, can be improved the conduction of the generating efficiency of solar battery
The manufacturing method of slurry and its manufacturing method and solar battery.
The solution to the problem
The research of people etc. is it is found that even if by (the Japanese Unexamined Patent Publication 2011-96747 public affairs of above patent document 1 according to the present invention
Report) and above patent document 2 (Japanese Unexamined Patent Publication 2005-243500 bulletin) contents combine, also do not generate synergy,
The generating efficiency of solar battery does not improve.I.e., it was found that even if frit (the tellurium system glass comprising tellurium oxide will have been used
Powder) electrocondution slurry in a part of frit be replaced into such as indium (In) powder, the generating efficiency of solar battery is also almost
Do not change.
However, the Japan for Japanese Patent Application 2016-161348 priority that the inventors of the present invention propose before opinion is special
It is willing to find in No. 2017-048982 and No. PCT/JP2017/010548, if having used obtained silver-colored tellurium cladding glass powder
Indium (In) powder is added in electrocondution slurry, then the solar battery of generating efficiency raising can be obtained.
The present invention is based on the above-mentioned opinions of the inventors of the present invention, as solution to the problems described above is used for, as described below.
That is,
Electrocondution slurry of the invention is characterized in that, coats glass comprising the electroconductive powder containing silver, indium powder, silver-colored tellurium
Powder, solvent and organic bond,
Above-mentioned silver tellurium cladding glass powder is that have on the surface of the tellurium glass frit of the tellurium containing 20 mass % or more with silver
Glass powder is coated with the silver-colored tellurium of tellurium clad as main component.
Relative to tellurium quality contained in above-mentioned silver-colored tellurium cladding glass powder, the use level of above-mentioned indium powder be preferably indium quality/
(the tellurium quality in indium quality+silver tellurium cladding glass powder) is in the range of 0.05~0.5.
It is preferred that above-mentioned tellurium glass frit contains selected from one or more of zinc, lead, bismuth, silicon and aluminium.
In addition, the manufacturing method of electrocondution slurry of the invention is characterized in that, there are following processes:
After the tellurium glass frit of tellurium containing 20 mass % or more is made an addition to silver complex solution, reducing agent is added,
Surface forms the process that silver-colored tellurium cladding glass powder is thus obtained with silver and tellurium clad as main component；And
Above-mentioned silver-colored tellurium cladding glass powder, the electroconductive powder containing silver, indium powder, solvent and organic bond are mixed
Process.
In addition, the manufacturing method of solar battery of the invention is characterized in that, has and print or apply on anti-reflection layer
Process cloth electrocondution slurry of the invention and be burnt into.
Invention effect
According to the present invention, it is possible to provide in the case where the electrode applications for solar battery, solar battery can be improved
Generating efficiency electrocondution slurry and its manufacturing method and solar battery manufacturing method.
Detailed description of the invention
Fig. 1 is ratio (turn of In/ (In+Te) and solar battery for showing the In mass in glass relative to tellurium quality
Change the chart of the relationship of efficiency.
Specific embodiment
(electrocondution slurry)
Electrocondution slurry of the invention include the electroconductive powder containing silver, indium (In) powder, silver-colored tellurium cladding glass powder, solvent,
And organic bond, further contain other ingredients as needed.
<electroconductive powder containing silver>
As the above-mentioned electroconductive powder containing silver, preferably there is the metal powder of silver powder or silver on surface or to conduction
The powder (for example, silver oxide) of silver is generated when slurry is heated.
The use level of the above-mentioned electroconductive powder containing silver in electrocondution slurry is preferably 70 mass % or more and 92 matter
Measure % or less.
Pass through the volume reference for the above-mentioned electroconductive powder containing silver that laser diffraction formula determination of particle size distribution measures
It is preferably 1 μm or more and 3 μm or less that 50% partial size (D50) is accumulated in particle diameter distribution
It as the shape of the above-mentioned electroconductive powder containing silver, is not particularly limited, can be suitable for selection according to purpose, it can be with
It is for example spherical, flat, rodlike, linear, irregular, or the different group of the combination of these shapes, average grain diameter
It closes.
<indium (In) powder>
Above-mentioned In powder is preferably metal In powder or the In powder containing silver.It is above-mentioned on the basis of having the effect of of the invention
Other elements other than In contained in In powder are preferably less than 20 mass %.In the present embodiment, In powder can be enumerated as gold
The case where belonging to In powder coats the powder of In powder but it is also possible to be In and silver-colored, alloy powder, by silver, can play same effect.
In the case where above-mentioned In powder contains silver, the electroconductive powder containing silver is correspondingly adjusted with the silver content (for example, silver
Powder) silver content.
As In contained in above-mentioned In powder and silver other than other elements, can contain conductive high element (for example,
Gold, copper, aluminium) or element to silicon as n-type dopant.
Above-mentioned In powder can be already oxidised for particle surface, but does not include whole as oxide powder (In2O3) In powder.
It is not particularly limited by the partial size (SEM partial size) of the above-mentioned In powder of scanning electron microscope (SEM) measurement, it can
It is suitable for selection according to purpose, preferably 1 μm or more and 40 μm hereinafter, in terms of used in the finger electrode in solar battery
It sets out, more preferably 1 μm or more and 10 μm or less.
It as the shape of above-mentioned In powder, is not particularly limited, can be suitable for selection according to purpose, it can be mentioned, for example: it is spherical, flat
It is flat-shaped, rodlike, linear, irregular etc..
It as the manufacturing method of above-mentioned In powder, is not particularly limited, can be suitable for selection according to purpose, following methods can be passed through
It obtains: in the high boiling solvent such as in tetraethylene glycol, by the heat/melting temperature to more than its fusing point of the ingot bar of In, in rouge
After carrying out strong stirring in the presence of fat acid, fatty acid amide etc., chilling is carried out.
It should be noted that aoxidizing in order to prevent, when manufacturing electrocondution slurry, above-mentioned In powder can be present in higher boiling
Cooperate in the state of in solvent.
<silver-colored tellurium cladding glass powder>
The surface of above-mentioned tellurium glass frit of the silver tellurium cladding glass powder in the tellurium (Te) containing 20 mass % or more have with
Silver and tellurium clad as main component.
About the details of above-mentioned silver-colored tellurium cladding glass powder, referring to Japanese Patent Application 2016-161348 specification the
[0012]~[0030]<tellurium glass frit>,<with silver and the tellurium clad as main component>recorded in section.In addition, about upper
The details for stating silver-colored tellurium cladding glass powder, referring to the Japanese Patent Application for the priority for having claimed Japanese Patent Application 2016-161348
Recorded in No. 2017-048982 and PCT/JP2017/010548 specification [0012]~[0036] section < tellurium glass frit
>,<with silver and tellurium clad as main component>.
Relative to the total amount of electrocondution slurry, use level of the above-mentioned silver tellurium cladding glass powder in electrocondution slurry is preferably 1 matter
Measure % or more and 5 mass % or less.When above-mentioned use level is less than 1 mass %, burn-through can be become inadequate, the string of solar battery
Connection resistance can be got higher.On the other hand, when above-mentioned use level is greater than 5 mass %, since resistance components increase, there are line resistance changes
The case where high, solar battery generating efficiency deteriorates.
Above-mentioned silver tellurium cladding glass powder such as has claimed the Japanese Patent Application of Japanese Patent Application 2016-161348 priority
No. 2017-048982 and No. PCT/JP2017/010548 recorded in specification such, exists on tellurium glass frit surface
With silver and tellurium substance as main component, is referred to silver and tellurium clad as main component, deposited on tellurium glass frit surface
With silver and tellurium substance as main component, above-mentioned to be referred to using silver and tellurium as main component, the summation of silver and tellurium is clad
In main component (50 mass % or more and 100 mass % or less).It should be noted that separately including 10 in above-mentioned clad
The Ag and Te of quality % or more.
The above-mentioned thickness with silver and tellurium clad as main component is preferably 10nm or more and 200nm hereinafter, more preferably
For 20nm or more and 150nm or less.
As the content of the tellurium in above-mentioned tellurium glass frit, as long as being 20 mass % or more, it is not particularly limited, it can root
It is suitable for selection according to purpose, in order to improve the generating efficiency (drop of the Ohmic resistance of electrode caused by burn-through resistance of solar battery
It is low), preferably 30 mass % or more, more preferably 40 mass % or more and 90 mass %.The content of above-mentioned tellurium is glimmering in utilization
In the case that light X-ray carries out composition analysis, as content contained in glass powder.
As the ingredient other than tellurium contained in above-mentioned tellurium glass frit, preferably comprise for example selected from bismuth (Bi), zinc (Zn),
Lithium (Li), sodium (Na), potassium (K), boron (B), silicon (Si), aluminium (Al), tungsten (W), molybdenum (Mo), manganese (Mn), iron (Fe), vanadium (V), phosphorus
(P), a kind in lead (Pb), antimony (Sb), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), titanium (Ti), zirconium (Zr) and lanthanum (La) with
On, further preferably selected from one or more of zinc, lead, bismuth, silicon and aluminium.
Tellurium in above-mentioned tellurium glass frit can be any form of oxide, metal and alloy, and oxide is preferably two
Tellurium oxide (TeO2)。
As the size distribution of above-mentioned silver-colored tellurium cladding glass powder, accumulation 10% partial size (D10) is preferably 0.1 μm or more and 10
μm hereinafter, more preferably 0.3 μm or more and 5 μm hereinafter, particularly preferably 0.5 μm or more and 2 μm or less.In addition, accumulation 50%
Partial size (D50) be preferably 0.1 μm or more and 20 μm hereinafter, more preferably 0.3 μm or more and 10 μm hereinafter, particularly preferably 1 μm
Above and 5 μm or less.In addition, accumulation 90% partial size (D90) is preferably 1 μm or more and 60 μm hereinafter, more preferably 1.5 μm or more
And 30 μm hereinafter, particularly preferably 1.5 μm or more and 20 μm or less.
The size distribution of above-mentioned silver tellurium cladding glass powder can be for example, by laser diffraction formula particle size distribution device (example
Such as, the Microtrac of Nikkiso Company Limited) measurement.
It as the BET specific surface area of above-mentioned silver-colored tellurium cladding glass powder, is not particularly limited, can be suitable for selection according to purpose,
Preferably 0.1m2/ g or more and 70m2/ g is hereinafter, more preferably 0.5m2/ g or more and 10m2/ g or less.
Above-mentioned BET specific surface area can be used to be measured such as commercially available BET specific surface area measurement device.
Above-mentioned silver tellurium cladding glass powder can be by the surface treating agent clad surface comprising organic matters such as fatty acid.
In terms of other than the above, glass powder is coated for silver tellurium used in the present invention, can refer to and have claimed Japan
In the Japanese Patent Application for the priority that Patent 2016-161348 2017-048982 and PCT/JP2017/010548 specification
The silver-colored tellurium of record coats glass powder.
It should be noted that being not limited to have claimed the Japanese Patent Application of Japanese Patent Application 2016-161348 priority
The silver-colored tellurium cladding glass powder recorded in No. 2017-048982 and PCT/JP2017/010548 specification, as long as to have silver
Powder with any one of the alloy, intermetallic compound and noncrystalline of tellurium is (for example, Japanese Patent Application 2016-006613 is said
Recorded in bright book silver cladding tellurium powder) and indium (In) powder both of which existing for mode constitute electrocondution slurry, so that it may play this hair
Bright effect.
Had as in electrocondution slurry using above-mentioned with the silver-colored tellurium of silver and tellurium clad as main component cladding glass
In the case where powder, compared with the tellurium glass frit for not having clad, the reasons why generating efficiency of solar battery can be improved, in advance
Want in the temperature band of the firing temperature lower than electrocondution slurry, silver is spread in the inside of tellurium glass frit, thus in tellurium system glass
Guiding path is easily formed in glass powder.In addition, since the viscosity of electrocondution slurry is difficult to be higher than the tellurium system glass without clad
Therefore glass powder it is small to reduce the necessity of viscosity to increase solvent (use level for reducing the electroconductive powder containing silver).Therefore recognize
For the electric conductivity of the conductive film after firing improves, as a result, improving the generating efficiency of solar battery.
Above-mentioned In powder can further improve the function of improving the generating efficiency of the solar battery of silver-colored tellurium cladding glass powder.
As the use level of above-mentioned In powder, relative to (being coated in glass powder for silver-colored tellurium in the present embodiment) tellurium in electrocondution slurry
Content (quality), indium quality/(the tellurium quality in indium quality+silver tellurium cladding glass powder) is preferably 0.05~0.5 range, more excellent
It is selected as 0.1~0.3 range.It is right when above-mentioned indium quality/(the tellurium quality in indium quality+silver tellurium cladding glass powder) is less than 0.05
The auxiliaring effect of burn-through almost disappears, and when being greater than 0.5, resistance components become more, therefore exist and adverse effect, solar battery occur
Generating efficiency deteriorate tendency.
It should be noted that " the tellurium content in silver-colored tellurium cladding glass powder " in the calculating of the In powder use level in the present invention
Refer to, the quality % of Te content obtained from glass powder carries out composition analysis will be coated multiplied by leading to silver-colored tellurium as fluorescent X-ray
It is worth obtained from the quality % of silver-colored tellurium cladding glass powder in plasma-based material.
That is, will coat glass powder in aftermentioned embodiment and comparative example to silver-colored tellurium by fluorescent X-ray and be formed
When the metals such as the tellurium other than silver in the value of the quality % of Te content obtained from analysis and silver-colored tellurium cladding glass powder are oxide
Value in the case where being calculated again according to the value is recorded together, but in the calculating of the In powder use level in above-mentioned electrocondution slurry,
Directly using the value of the quality % of the tellurium content of the analysis result using fluorescent X-ray.
The power generation that combination as above-mentioned In powder and above-mentioned silver-colored tellurium cladding glass powder can further improve solar battery is imitated
The reasons why rate, thus it is speculated that temperature when for firing rises, the oxygen of the anti-reflection layer of solar battery, i.e. SiN layer and tellurium or tellurium
Compound reacts (burn-through), forms guiding path, while causing the diffusion of silver, it is ensured that conducting.At this point, In and silver and tellurium alloy,
Solution temperature is reduced, above-mentioned reaction is thus caused.Or it is considered closely exist due to each metal, it is easier to cause anti-
It answers, the electric conductivity of the conductive film after firing and the electric conductivity as solar battery improve, as a result, improving solar-electricity
The generating efficiency in pond.
<organic bond>
As above-mentioned organic bond, as long as can be used as the electrode applications as solar battery, near 800 DEG C
The organic bond with pyrolytic of the resin combination of firing, is just not particularly limited, and well known resin can be used, can
It enumerates for example: the cellulose derivatives such as methylcellulose, ethyl cellulose, hydroxymethyl cellulose, polyvinyl alcohol, polyvinyl
Pyrrolidinone compounds, acrylic resin, alkyd resin, acrylic resin, polyvinyl chloride resin, polyurethane series resin, rosin series
Resin, terpenic series resin, phenolic aldehyde system resin, fatty family Petropols, vinyl acetate resin, vinyl acetate-acrylic
The organic bond etc. of the butyral resins derivative such as acid ester copolymer, polyvinyl butyral.These resins can be used alone 1
Kind, two or more use can also be combined.
<solvent>
As long as above-mentioned solvent can dissolve above-mentioned organic bond, it is not particularly limited, well known solvent can be used, leading
In the manufacture of plasma-based material, preferably above-mentioned organic bond is dissolved and is used in mixed way in advance.
As above-mentioned solvent, it can be mentioned, for example: the molten fibre of dioxanes, hexane, toluene, ethyl cellosolve, cyclohexanone, butyl
Agent, butyl cellosolve acetate, butyl carbitol, acetate of butyl carbitol, diethylene glycol diethyl ether, diacetone alcohol, pine
Lipidol, methyl ethyl ketone, benzylalcohol, 2,2,4- trimethyl -1,3- pentanediol only son's acid esters etc..These solvents can be used alone,
Two or more use can be combined.
<other ingredients>
As above-mentioned other ingredients, it can be mentioned, for example: surfactant, dispersing agent, viscosity modifier etc..
(manufacturing method of electrocondution slurry)
The manufacturing method of electrocondution slurry of the invention has following processes:
After the tellurium glass frit of tellurium containing 20 mass % or more is made an addition to silver complex solution, reducing agent is added,
Surface forms the process that silver-colored tellurium cladding glass powder is thus obtained with silver and tellurium clad as main component；And
By above-mentioned silver-colored tellurium cladding glass powder, electroconductive powder, indium (In) powder, solvent and organic bond containing silver
Mixed process further has other process as needed.
About the above-mentioned process for obtaining silver-colored tellurium cladding glass powder, Japanese Patent Application 2016-161348 specification the can refer to
[0031]~[0042] " manufacturing method of silver-colored tellurium cladding glass powder " recorded in section.In addition, obtaining silver-colored tellurium cladding about above-mentioned
The process of glass powder can refer to and have claimed Japanese Patent Application 2017-048982 of priority of Japanese Patent Application 2016-161348
And " the manufacturer of silver-colored tellurium cladding glass powder recorded in PCT/JP2017/010548 specification [0037]~[0048] section
Method ".
It should be noted that above-mentioned In powder can directly add in the slurry, glass powder can also be coated with silver-colored tellurium in advance
It is added after mixing.
It as above-mentioned mixed process, is not particularly limited, can be suitable for selection according to purpose, for example, can be used super
Sound wave dispersion, disperser, three-roll grinder, ball mill, ball mill, Dual-screw kneader, rotation/revolution type blender etc. will contain
There are electroconductive powder, indium powder, silver-colored tellurium cladding glass powder, organic bond, solvent and the other ingredients used as needed of silver
Mixing.
Using cone plate type viscometer, under conditions of 25 DEG C, 1rpm value, so that the viscosity of above-mentioned electrocondution slurry is preferably
100Pas or more and 1000Pas mode below adjusts each use level.When above-mentioned viscosity is less than 100Pas, in low viscosity
Region can occur " to ooze out ", be greater than 1000Pas when, highly viscous region can occur referred to as " fuzzy " printing not
Good situation.
Above-mentioned electrocondution slurry containing silver-colored tellurium cladding glass powder and In powder of the invention, can compared with existing electrocondution slurry
It is preferably used as being used to form the electrocondution slurry of the electrode of firing type solar battery, the electrode of various electronic components, circuit etc..
(manufacturing method of solar battery)
The manufacturing method of solar battery of the invention, which has, prints on anti-reflection layer or is coated with conductive paste of the invention
The process expected and be burnt into further has other process as needed.
Above-mentioned anti-reflection layer is made on silicon.
It is manufactured by the solar battery that the manufacturing method of above-mentioned solar battery obtains using electrocondution slurry of the invention,
Therefore, contact resistance can be further decreased, good characteristic of solar cell is obtained.
Embodiment
Hereinafter, being illustrated to the embodiment of the present invention, but the present invention is not by any restriction of these embodiments.
(embodiment 1)
The production-of silver-colored tellurium cladding glass powder
Prepare 10g tellurium glass frit, composition is Te:69.5 mass %, Bi using the analysis result of fluorescent X-ray:
23.8 mass %, Zn:6.8 mass %, if calculated with oxide, for TeO2: 67.4 mass %, Bi2O3: 25.5 mass %,
ZnO:7.0 mass %, and 334 DEG C of softening point, density 5.2g/cm3。
Jeol Ltd.'s system, JSX-3201 are used using the analysis of above-mentioned fluorescent X-ray, with voltage 30kV, electricity
0.080mA, analysis time 400sec, path: Air is flowed to carry out.It is same as below.
The silver nitrate aqueous solution 3.47g that silver content is 32 mass % is mixed in the state of being stirred to pure water 787g
1L beaker in, be diluted, the silver nitrate aqueous solution containing silver 1.11g be made.
Then, the ammonium hydroxide 2.5g that the 28 mass % as complexing agent are added into the beaker, obtains silver-colored amine complex salt aqueous solution
(pH 11).After the liquid temperature of the silver amine complex salt aqueous solution is set as 30 DEG C, above-mentioned tellurium glass frit 10g is put into.It throws immediately after
Enter as the hydrazine 0.3g of reducing agent, silver colloid, [solvent is pure water, utilizes transmission electron microscope (TEM) measurement in advance
The partial size (TEM partial size) of contained nanoparticle silver is 5nm~40nm, and nanoparticle silver content is 0.01g (relative in aqueous solution
Silver content be 0.001 times)] mixture that is obtained by mixing of 10.3g and pure water 20g, by the curing time (in order to not residual in liquid
Stay the time for not restoring silver and waiting) it is set as 5 minutes, it will be with silver and tellurium clad layer-forming as main component in above-mentioned tellurium system glass
Glass powder surface.
Reducing agent has been put into after five minutes, is carried out attraction filtering to the slurry containing silver cladding glass powder, is carried out using pure water
Washing, the conductivity of liquid reaches 0.5mS/m hereinafter, having obtained filter cake after cleaning.Vacuum by obtained filter cake at 75 DEG C
It is 10 hours dry in drying machine, it has obtained having for embodiment 1 and glass is coated with the silver-colored tellurium of silver and tellurium clad as main component
Glass powder.
The pH of filtrate when above-mentioned attraction is filtered is 9.6, when carrying out ICP luminesceence analysis (SII corporation, SPS5100), Te
For 89.7ppm.
Next, carrying out composition analysis to obtained silver-colored tellurium cladding glass powder using fluorescent X-ray, it is known that Ag:17.3 matter
Measure %, Te:56.0 mass %, Bi:20.9 mass %, Zn:5.9 mass %.
Herein, if calculating content in the form of the oxide to the composition other than Ag, for Ag:14.6 mass %, TeO2:
59.4 mass %, Bi2O3: 19.8 mass %, ZnO:6.2 mass %.
Next, the measurement of many characteristics is carried out to obtained silver-colored tellurium cladding glass powder as described below.It shows the result in
Table 1.
[size distribution]
For the size distribution of silver-colored tellurium cladding glass powder, by laser diffraction formula size distribution device, [day machine fills the meeting of strain formula
The Microtrac particle size distribution device (Microtrac corporation, MT3300EXII) of society] it is measured, find out accumulation
10% partial size (D10), accumulation 50% partial size (D50) and accumulation 90% partial size (D90).
[BET specific surface area]
For silver-colored tellurium cladding glass powder BET specific surface area, using specific area measuring device (device name: Macsorb,
Mountech corporation) and be measured by the BET1 point method using nitrogen adsorption.It should be noted that in BET specific surface
In long-pending measurement, the degassing conditions before measurement are set as at 60 DEG C 10 minutes.
The production-of-In powder
In the tetraethylene glycol 100g as solvent, the ingot bar 96g of the 99.99 mass % of In is heated to 170 DEG C, makes In
After fusing, the double capric acid of addition vinyl, after carrying out strong stirring with 710rpm, chilling is thus obtained to include metal In's
In powder.
The SEM partial size of obtained In powder is 10 μm~400 μm, by the sieve of 150 mesh, makes 10 μm~100 μm of partial size.
Next, having made electrocondution slurry as described below using obtained silver-colored tellurium cladding glass powder and In powder.
The production-of electrocondution slurry
Weigh above-mentioned silver-colored tellurium cladding glass powder (17.3 mass % of silver content) 1.677 mass %, silver powder (DOWA High
Tech Co. Ltd. system, AG-2.5-8F, accumulation 50% partial size (D50)=1.5 μm) 90.0 mass %, above-mentioned 0.096 matter of In powder
Amount %, (ethyl cellulose 10cps 30 mass % (Wako Pure Chemical Industries, Ltd.'s system) acetate of butyl carbitol is molten for carrier
Liquid) 0.41 mass %, carrier (EU-5638,46.1 mass % acetate of butyl carbitol solution of acrylic resin, Japan's carbonization
Object Industrial Co., Ltd system) 2.40 mass %, solvent (CS-12, JNC Corporation's system, Texanol) 3.11 mass %, solvent
(Wako Pure Chemical Industries, Ltd.'s system, acetate of butyl carbitol) 1.54 mass %, magnesium stearate (and Wako Pure Chemical Industries strain formula
Commercial firm's system) 0.51 mass % of 0.26 mass % and oleic acid (Wako Pure Chemical Industries, Ltd.'s system), is stirred by rotation/revolution type
It mixes after device (Co., Ltd.'s Thinky system, ARE-310) mixed (pre- be kneaded), passes through 3 rollers (EXAKT corporations, M-
It 80S) is kneaded, results in electrocondution slurry.
In the composition analysis carried out using fluorescent X-ray to silver-colored tellurium cladding glass powder, Te content is 56.0 mass %, because
This, the Te mass in silver-colored tellurium cladding 1.677 mass % of glass powder is 0.94 mass %, In amount (0.096 matter relative to In powder
Measure %), it is In mass/(In mass+silver tellurium coats the tellurium quality in glass powder)=0.09.
After measuring the obtained viscosity of electrocondution slurry, with its viscosity it is correspondingly appropriate to amount of slurry (in embodiment 1 for
0.35 mass %) additional Texanol and butyl carbitol mass ratio 1:1 mixed solvent, viscosity is adjusted, thus in viscosimeter
1 under (Brookfield corporation, HBDV-IIIULTRA) middle cone-plate using CPE-52,5 minutes values lower to 1rpm and 5rpm
When the value of minute is determined, the viscosity at 1rpm is 290 ± 20Pas, and the viscosity at 5rpm is 70 ± 2Pas.
Utilize the print of 1 minute value bring high quality by 5 minutes values at 1rpm within the scope of this and at 5rpm
Map brushing case carries out the performance evaluation of electrocondution slurry as described below.Show the result in table 2.
Using obtained electrocondution slurry, solar battery has been made as described below.
<production of solar battery>
On silicon for solar cell substrate (105 Ω/), screen process press (Micro Tech corporation, MT- are utilized
320T), 154mm is formd using aluminum slurry (Japan's aluminium Co. Ltd. system, Al solar 14-7021) on substrate back
Solid pattern.
Using air drier, dried 10 minutes with 200 DEG C.
The electrocondution slurry of embodiment 1 is used in substrate surface, forms 40 μm of wide finger electrodes and 3 bus bar electrodes.
Using air drier, dried 10 minutes with 200 DEG C.
It is burnt into IR furnace (NGK Insulators Ltd's system) using high speed, the temperature (firing temperature) when by peak value is set as 820
DEG C, high speed has been carried out with in-out 21sec and has been burnt into.Solar battery has been made as described above.
<evaluation of characteristic of solar cell>
For the solar battery of production, characteristic of solar cell is evaluated using WACOM corporation solar simulator.
The transfer efficiency of obtained solar battery is 18.86% at 820 DEG C of firing temperature.Show the result in table 2.
<evaluation of volume resistivity>
Silk-screen printing is carried out to the electrocondution slurry of embodiment 1 on Si substrate under the following conditions, forms conductive film.
Printing equipment: Micro Tech corporation MT-320T
Version: 500 μm of line width, coiling 37.5mm, 250 mesh, 23 μm of linear diameter
Printing condition: blade pressure 180Pa, print speed printing speed 80mm/s, gap 1.3mm
Using atmospheric circulation type drying machine, obtained film is heated with 10 minutes conditions at 150 DEG C.
Next, being burnt into 820 DEG C of peak temperature, in-out21sec using high speed firing furnace, having made conductive film.
Next, using surface roughness meter (Tokyo Seimitsu Co., Ltd's system, SURFCOM for the conductive film that will be obtained
480B-12) difference in height for not being printed with the part and the part of conductive film of film on Si substrate is measured, thus measure conductive film
Average thickness.
Next, determining length (interval) position of conductive film using digital multimeter (Co., Ltd.'s ADC system, R7451A)
The resistance value set.According to the volume that the size (average thickness, width, length) of each conductive film finds out conductive film, according to the volume
The volume resistivity of conductive film is found out with the resistance value of measurement, is 1.88 μ Ω cm.
(embodiment 2)
Be in embodiment 1, Te:51.3 mass % using the analysis result of fluorescent X-ray to the composition of tellurium glass frit,
Pb:38.6 mass %, Zn:10.0 mass % and contain lead, and 421 DEG C of the softening point of tellurium glass frit, density 5.1g/cm3,
In addition to this, silver-colored tellurium cladding glass powder has been obtained similarly to Example 1.
Next, carrying out composition analysis to obtained silver-colored tellurium cladding glass powder (containing Pb) using fluorescent X-ray, it is known that its
Contain Ag:10.4 mass %, Te:46.3 mass %, Pb:34.1 mass %, Zn:9.2 mass %.
If calculating the content of the composition other than Ag, in the form of the oxide similarly to Example 1 for Ag:9.4 matter
Measure %, TeO2: 48.1 mass %, PbO:32.6 mass %, ZnO:9.9 mass %.
In addition, having carried out the measurement of many characteristics of silver-colored tellurium cladding glass powder similarly to Example 1.Show the result in table
1。
The pH of filtrate is 9.6, when carrying out ICP luminesceence analysis (SII corporation, SPS5100), Te 93ppm, Pb 1ppm
Below.
Next, production is led similarly to Example 1 other than the silver-colored tellurium used coats glass powder (containing Pb)
Plasma-based material, appropriate to amount of slurry (mass ratio 1 of Texanol and butyl carbitol are added for 0.42 mass %) in example 2:
1 mixed solvent, so that in the mode that the viscosity under 1rpm is 290 ± 20Pas, the viscosity at 5rpm is 70 ± 2Pas
Viscosity adjustment is carried out.
Composition analysis is carried out to silver-colored tellurium cladding glass powder using fluorescent X-ray, Te content is 46.3 mass %.Therefore, silver-colored
It is 0.78 mass % that tellurium, which coats the Te Mass Calculation in 1.677 mass % of glass powder to go out, relative to 0.096 mass % of In powder, is
In mass/(the tellurium quality in In mass+silver tellurium cladding glass powder)=0.11.
Next, making solar battery similarly to Example 1, characteristic of solar cell is evaluated.It will knot
Fruit is shown in table 2.
The transfer efficiency of obtained solar battery is 18.55% at 820 DEG C of firing temperature.
In addition, the volume resistivity of conductive film is 1.98 μ Ω cm.
(comparative example 1)
In embodiment 1, In powder is not added, and the use level of silver-colored tellurium cladding glass powder is set as 1.77 mass %, removes this
In addition, electrocondution slurry and solar battery are made similarly to Example 1, to the performance and characteristic of solar cell of electrocondution slurry
It is evaluated.Show the result in table 2.
The transfer efficiency of obtained solar battery is 18.68% at 820 DEG C of firing temperature.In addition, the body of conductive film
Product resistivity is 2.03 μ Ω cm.
(comparative example 2)
In example 2, In powder is not added, and the use level of silver-colored tellurium cladding glass powder (containing Pb) is set as 1.77 matter
% is measured, in addition to this, electrocondution slurry and solar battery are made similarly to Example 2, to the performance and the sun of electrocondution slurry
Energy battery behavior is evaluated.Show the result in table 2.
The transfer efficiency of obtained solar battery is 18.38% at 820 DEG C of firing temperature.In addition, the body of conductive film
Product resistivity is 1.92 μ Ω cm.
(comparative example 3)
In embodiment 1, silver is replaced used as the 1.6 mass % of tellurium glass frit of the raw material of silver-colored tellurium cladding glass powder
Tellurium coat glass powder, and by silver powder (DOWA High Tech Co. Ltd. system, AG-2.5-8F, accumulation 50% partial size (D50)=
1.5 μm) it is set as 90.2 mass %, In powder is set as to 0.1 mass % (In mass/(the tellurium quality in In mass+tellurium glass frit)
=0.1) electrocondution slurry and solar battery, in addition to this, are made similarly to Example 1, performance to electrocondution slurry and too
Positive energy battery behavior is evaluated.Show the result in table 2.
The transfer efficiency of obtained solar battery is 18.50% at 820 DEG C of firing temperature.In addition, the body of conductive film
Product resistivity is 2.00 μ Ω cm.
(comparative example 4)
In comparative example 3, In powder is not added, in addition to this, electrocondution slurry and solar-electricity is made in the same manner as comparative example 3
The performance of electrocondution slurry and characteristic of solar cell are similarly to Example 1 evaluated in pond.Show the result in table 2.
The transfer efficiency of obtained solar battery is 18.51% at 820 DEG C of firing temperature.In addition, the body of conductive film
Product resistivity is 1.98 μ Ω cm.
(comparative example 5)
In comparative example 3, indium oxide powder (Tech plants of formula meetings of DOWA High are added in a manner of keeping the use level of In identical
Society's system) 0.121 mass % replaces In powder, and by silver powder (DOWA High Tech Co. Ltd. system, AG-2.5-8F, accumulation
50% partial size (D50)=1.5 μm) 90.2 mass % are set as, in addition to this, electrocondution slurry and too is made in the same manner as comparative example 3
Positive energy battery, similarly to Example 1 evaluates the performance of electrocondution slurry and characteristic of solar cell.It shows the result in
Table 2.
The transfer efficiency of obtained solar battery is 18.27% at 820 DEG C of firing temperature.In addition, the body of conductive film
Product resistivity is 1.99 μ Ω cm.
(comparative example 6)
In embodiment 1, glass powder is set as commercially available product ASF-1898B (Asahi Glass Co., Ltd's system (boron without containing tellurium
Silicate glasses, 438 DEG C of softening point, density 3.4g/cm3), in addition to this, silver-colored cladding glass has been obtained similarly to Example 1
Powder.In this case, due to not containing tellurium in glass powder, glass surface is coated by silver.
In order to carry out embodiment 1 electrocondution slurry comparative evaluation, weigh silver powder (DOWA High Tech Co., Ltd.
System, AG-2.5-8F, accumulation 50% partial size (D50)=1.5 μm) 87.6 mass %, In powder, 0.10 mass %, tellurium dioxide (and light
Chun Yao Industrial Co., Ltd system) 2.4 mass % (In mass/(In mass+tellurium quality)=0.05), above-mentioned silver cladding glass powder
1.58 mass %, as burn auxiliary agent bismuth oxide (DOWA High Tech Co. Ltd. system) 0.19 mass %, carrier (ethyl
Cellulose 10cps30 mass % (Wako Pure Chemical Industries, Ltd.'s system) acetate of butyl carbitol solution) 0.41 mass %, load
Body (EU-5638,46.1 mass % acetate of butyl carbitol solution of acrylic resin, Nippon Carbide Kogyo K.K's system)
2.38 mass %, solvent (CS-12, JNC Corporation's system, Texanol) 1.56 mass %, solvent (and Wako Pure Chemical Industries strain formula
Commercial firm's system, acetate of butyl carbitol) 3.03 mass %, magnesium stearate (Wako Pure Chemical Industries, Ltd.'s system) 0.25 matter
% and 0.51 mass % of oleic acid (Wako Pure Chemical Industries, Ltd.'s system) is measured, makes electrocondution slurry similarly to Example 1, it is right
The performance of electrocondution slurry is evaluated.
Next, making solar battery similarly to Example 1, characteristic of solar cell is evaluated.It will knot
Fruit is shown in table 2.The transfer efficiency of obtained solar battery is 17.83% at 820 DEG C of firing temperature.In addition, conductive film
Volume resistivity is 2.63 μ Ω cm.
(comparative example 7)
In comparative example 6, In powder is not added, and the cooperation of silver cladding glass powder is set as 1.68 mass %, in addition to this,
Electrocondution slurry and solar battery are made in the same manner as comparative example 6, similarly to Example 1 to the performance of electrocondution slurry and the sun
Energy battery behavior is evaluated.Show the result in table 2.
The transfer efficiency of obtained solar battery is 17.85% at 820 DEG C of firing temperature.In addition, the body of conductive film
Product resistivity is 2.68 μ Ω cm.
[table 1]
[table 2]
According to above-mentioned result it is found that the electrocondution slurry of the silver-colored tellurium cladding glass powder of the cooperation of embodiment 1 and 2 and In powder with
The case where in the case where without using In powder or using without with the silver-colored tellurium glass frit with tellurium clad as main component
It compares, the low conductive film of volume resistivity can be obtained, further have the effect of improving the transfer efficiency of solar battery.
In addition, by comparing example 3 compared with comparative example 4 it is found that in the case where no silver-colored tellurium cladding, even if addition In
Powder, the transfer efficiency of solar battery, the volume resistivity of conductive film also almost do not observe difference.
In addition, by comparing example 3~5 comparison it is found that even if addition oxidation In powder, the transfer efficiency of solar battery,
The volume resistivity of conductive film does not also improve, deteriorates instead.It is also the same in silver-colored tellurium cladding glass to envision this.
In addition, by Examples and Comparative Examples 6 with 7 compared with it is found that in glass do not contain tellurium in the case where, even if
In the case where having used silver cladding glass powder obtained from being carried out similarly silver-colored cladding processing, the addition effect of In powder is not observed yet
Fruit.
Next, in embodiment 1, changing the ratio between In powder and silver-colored tellurium cladding amount of glass, making indium (In) quality/(indium (In)
Tellurium (Te) quality in quality+silver tellurium cladding glass powder) variation, in addition to this, similarly to Example 1 in electrocondution slurry
The proper range of the In amount of addition is investigated, and table 3 and Fig. 1 are shown the result in.
[table 3]
According to the result of table 3 and Fig. 1 it is found that use level as In powder, relative to institute in above-mentioned silver-colored tellurium cladding glass powder
The tellurium quality contained, indium quality/(the tellurium quality in indium quality+silver tellurium cladding glass powder) preferred scope is 0.05~0.5, more preferably
Range is 0.1~0.3.
Industrial applicibility
Silver-colored tellurium cladding glass powder of the invention can be used as the electrocondution slurry for being used to form the electrode of various electronic components, circuit
Material, the particularly preferably electrocondution slurry of the electrode as solar battery.
Claims (5)
1. a kind of electrocondution slurry, which is characterized in that
Glass powder, solvent and organic bond are coated comprising the electroconductive powder containing silver, indium powder, silver-colored tellurium,
The silver tellurium cladding glass powder is that have on the surface of the tellurium glass frit of the tellurium containing 20 mass % or more with silver and tellurium
The silver-colored tellurium of clad as main component coats glass powder.
2. electrocondution slurry according to claim 1, which is characterized in that
Relative to tellurium quality contained in the silver-colored tellurium cladding glass powder, the use level of the indium powder be indium quality/(indium quality+
Tellurium quality in silver-colored tellurium cladding glass powder) in the range of 0.05~0.5.
3. electrocondution slurry according to claim 1 or 2, which is characterized in that
The tellurium glass frit contains selected from one or more of zinc, lead, bismuth, silicon and aluminium.
4. a kind of manufacturing method of electrocondution slurry, which is characterized in that including following processes:
After the tellurium glass frit of tellurium containing 20 mass % or more is made an addition to silver complex solution, reducing agent is added, on surface
Form the process that silver-colored tellurium cladding glass powder is thus obtained with silver and tellurium clad as main component；And
The work that the silver-colored tellurium cladding glass powder, the electroconductive powder containing silver, indium powder, solvent and organic bond are mixed
Sequence.
5. a kind of manufacturing method of solar cell, which is characterized in that
With electrocondution slurry according to any one of claims 1 to 3 is printed or is coated on antireflection layer and is burnt into
Process.
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| PCT/JP2017/031968 WO2018047822A1 (en) | 2016-09-08 | 2017-09-05 | Conductive paste, method for producing same, and method for producing solar cell |
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| CN114944238A (en) * | 2022-07-27 | 2022-08-26 | 西安宏星电子浆料科技股份有限公司 | Glass paste for conductive silver paste, preparation method of conductive silver paste and solar cell |
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| CN109807346A (en) * | 2019-02-18 | 2019-05-28 | 贵州理工学院 | A kind of glass flour complexes and preparation method thereof of silver tellurium cladding |
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| JP6236557B1 (en) * | 2016-03-18 | 2017-11-22 | Ｄｏｗａエレクトロニクス株式会社 | Silver tellurium-coated glass powder and method for producing the same, and conductive paste and method for producing the same |
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2016
- 2016-09-08 JP JP2016175884A patent/JP6246877B1/en not_active Expired - Fee Related
-
2017
- 2017-09-05 WO PCT/JP2017/031968 patent/WO2018047822A1/en active Application Filing
- 2017-09-05 US US16/330,878 patent/US10833209B2/en active Active
- 2017-09-05 KR KR1020197009603A patent/KR20190052029A/en not_active Application Discontinuation
- 2017-09-05 CN CN201780054325.XA patent/CN109661707B/en active Active
- 2017-09-07 TW TW106130647A patent/TWI637403B/en not_active IP Right Cessation
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| CN114944238A (en) * | 2022-07-27 | 2022-08-26 | 西安宏星电子浆料科技股份有限公司 | Glass paste for conductive silver paste, preparation method of conductive silver paste and solar cell |
Also Published As
| Publication number | Publication date |
|---|---|
| US20190189810A1 (en) | 2019-06-20 |
| CN109661707B (en) | 2020-08-25 |
| TW201812794A (en) | 2018-04-01 |
| TWI637403B (en) | 2018-10-01 |
| JP2018041663A (en) | 2018-03-15 |
| JP6246877B1 (en) | 2017-12-13 |
| WO2018047822A1 (en) | 2018-03-15 |
| US10833209B2 (en) | 2020-11-10 |
| KR20190052029A (en) | 2019-05-15 |
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